Photosensitive compositions comprising a photosensitive polymer and a photochromic compound

ABSTRACT

wherein R1 represents a hydrogen atom or a methyl group; R2 represents a hydrogen atom, a cyano group or a -COOR group in which R represents a hydrogen atom or an alkyl group having from 1 to 6 carbon atoms; R3 represents a   A photosensitive composition comprising (1) a photosensitive high molecular weight compound having therein at least one of the units represented by the following general formulae (I) to (V)

United States Patent [191 Osada et al.

[ PHOTOSENSITIVE COMPOSITIONS COMPRISING A PHOTOSENSITIVE POLYMER AND A PHOTOCHROMIC COMPOUND Inventors: Chiaki Osada; Masato Satomura;

Hisatake Ono, all of Osaka, Japan [73] Assignee: Fuji Photo Film Company, Ltd.,

Kanagawa, Japan Filed: June 23, 1972 Appl. No.: 265,888

[30] Foreign Application Priority Data June 23, 1971 Japan 46-45382 US. Cl 96/90 PC, 96/33, 96/35.1, 96/115 R, 204/l59.l4, 204/15918 Int. Cl G03c 1/70 Field of Search 96/115 R, 90 PC; 204/l59.l4, 159.18

[56] References Cited UNITED STATES PATENTS 12/1967 Wu 96/115R 3/l972 Delzenne et al. 96/115 R 2/1972 Poot et al. 96/90 PC Primary Examiner-Ronald H. Smith v Attorney, Agent, or Firm-Sughrue, Rothwell, Mion, Zinn & Macpeak [57] ABSTRACT A photosensitive composition comprising (i) a photosensitive high molecular weight compound having therein at least one of the units represented by the following general formulae (I) to (V) c) R: (II) 1 Apr. 16, 1974 wherein R represents ahydrogen atom or a methyl group; R represents a hydrogen atom, a cyano group or a -COOR group in which R represents a hydrogen atom or an alkyl group havingfrom l to 6 carbon atoms; R represents a group, a

group, a NJ group, or a group in which R represents a hydrogen atom, a halogen atom, a nitro group, a methyl group, an ethyl group, a methoxy group or an ethoxy group; R represents a hydrogen atom, an alkyl group having from 1 to 6 carbon atoms, or a halogenated alkyl group; R represents a -CH CI-ll group, .a -CH CH- group, or a 34 Claims, 4 Drawing Figures PATENTEDAPR 16 1974 FIG. .I

400 WAVE LENGTH (mp) FIG 2 552mm 25mm WAVELENGTH (mp) "MIIIIIIII'IZ PI-IOTOSENSITIVE COMPOSITIONS COMPRISING A PHOTOSENSITIVE POLYMER AND A PHOTOCIIROMIC COMPOUND BACKGROUND OF THE INVENTION l. FIELD OF THE INVENTION The present invention relates to a photosensitive composition mainly comprising a photosensitive resin having a cinnamoyl group, a B-(2-furyl)acryloyl group or a B-(pyridyUacryloyl group as side chains, an indolinospirobenzopyran derivative which can generate an image coloration immediately upon light exposure, and a sensitizer. More specifically, the present invention relates to a photosensitive composition which shows a strong adhesive property to metals and forms on a metal. surface a photosensitive film or layer which ishardly strippable by rubbing.

2. DESCRIPTION OF THE PRIOR ART A polyvinyl cinnamate type photosensitive resin has been widely used as an excellent photosensitive resin but it is poor in its adhesive properties to metals. Accordingly, although such a photosensitive resin is excellent in a system not subjected to abrasion, such as a photoresist, it is unsuitable for a system encountering severe abrasion, such as printing plates.

The light exposure and the development of a presensitized lithographic plate are generally carried out as separate operational steps. Therefore, if the latent image formed by the light exposure can be seen, it is quite convenient and such difficulties as double exposure can be prevented. Also, when various kinds of images are printed on a large sheet of photosensitive ma terial, the positions of the images to be printed can be determined readily and at the same time such difficulties as double exposure and blank printing can be prevented if the latent image obtained upon light exposure can be seen.

SUMMARY OF THE INVENTION The inventors have succeeded in discovering novel photosensitive resins unaccompanied by such difficulties as described above and a photochromic compound is incorporated in the, composition containing such a photosensitive resin for forming a visual latent image immediately upon light exposure.

wherein R represents H or CH R represents H, CN, or COOR (where R is H or an alkyl group having from 1 to 6 carbon atoms); R represents ing from 1 to 6 carbon atoms. or a halogenated alkyl group; R represents -CH -CH -CH=CI I--, or

X represents 0 or NH; n is an integer of from 1 to I 4; and". is an integer of from 1 to 6. F

BRIEF DESCRIPTION OF THE ACCOMPANYING DRAWINGS FIG. 1 shows the characteristic curves obtained for a diazo compound and for a indolinobenzospiropyran compound. I

FIG. 2 shows the wave length region for the light hardening of the photosensitive composition of this invention and the characteristic curve of the spiropyran compound used in this invention. I

FIG. 3 and 4 are schematic views showing two embodiments of photosensitive materials employing the photosensitive compositions of this invention.

DETAILED DESCRIPTION OF THE INVENTION In regard to a lithographic printing plate which can providevisible images immediately after light exposure, Japanese Pat. Publication No. 6413/1969, discloses a diazo compound used as the photosensitive material. However, when a diazo compound is used for such a purpose with a spiropyran compound, the effective energy will be absorbed by the spiropyran compound to suppress the occurence of the photoreaction of the diazo compound since the photosensitive wave length region of the diazo compound almost coincides with the photosensitive wave length region of the spiropyran compound. This results in reducing the sensitivity of the diazo compound. Consequently, the diazo compound. composition containing the spiropyran compound requires a light exposure time of from 2 to 3 times that of the diazo compound composition containing no such spiropyran compound. In FIG. 1 of the accompanying drawing the photosensitive wave length region of a diazo compound and the photosensitive spiropyran compound are shown. In the figure, curve :11 shows the photosensitive wave length region of a general diazo compound and curve 12 shows the photosensitive wave length region of a general indolinobenzospiropyran compound.

The polyvinyl cinnamate used in Example of Japanese Pat. Publication No. 6413/1969 referred to above has the disadvantage that it is unsuitable for the lithographic printing material as stated in the present invention due to poor printability.

plate is prepared by applying to a support a composition of the photosensitive resin having added thereto a sensitizer and an indolinobenzospiropyran compound.

That is to say, in contrast to the case of the diazo compounds, the photosensitive resin used in this invention can be spectrally sensitizedby using a sensitizer, whereby it has a sensitivity at a longer wave than the photosensitive wave length region of the spiropyran compound. In the photosensitive composition of this invention the coloring of the spiropyran compound occurs by light of different wave length than that of the light for hardening the. photosensitive resin and thus a visual latent image can be formed without reducing the sensitivity of the photosensitive resin.

Furthermore, when a diazo compound is used, it is impossible to dissolve off the spiropyran compound in the resin remaining on the metallic sheet as the image since the treatment after the light exposure is generally conducted in an aqueous system. On the other hand, because by employing the photosensitive composition of this invention the treatment after the light exposure is generally conducted in an aqueous solvent system, the spiropyran compound remaining in the resin can be dissolved off, which prevents the occurrence of various difficulties in the subsequent processing steps.

In FIG. 2 of the accompanying drawings the photosensitive wave length region for the light hardening of the photosensitive composition of this invention as curve 21 and the photosensitive wave length region of the spiropyran compound as curve 22 are shown.

In the figure, the shaded portion shows the photosensitive wave length region in which the light hardening reaction occurs without being influenced by the spiropyran compound.

Furthermore, when the photosensitive composition of this invention is used for a lithographic printing plate, the printability of the lithographic printing plate is superior to conventional lithographic printing plates as shown in the following table.

Printability Photosensitive Layer (number of printed copies) Photosensitive Composition 100,000 of this Invention Polyvinyl Cinnamate 20,000 Diazo Compound 40,000

The photosensitive resin used in this invention is quite excellent in adhesive properties to metals, printability, and grease receptivity in comparison with a conventional polyvinyl cinnamate as described in Example 5 of Japanese Pat. Publication No. 6413/1969.

als can be used at a level of from about 2 to 35 percent by weight, preferably from about to 25 percent by weight, based on the total amount of the polymer.

,The homopolymers and copolymers of this invention suitably can have molecular weights ranging from 5,000 to 50,000 preferably, from 10,000 to 25,000.

Examples of the spiropyran compounds which can be used in this invention are l,3,3-trimethyl-6'- nitrobis(indoline-2,2-benzopyran); 1,3,3-trimethyl-6- nitro-8'-methoxyspiro(indoline-2,2'-benzopyran); 1,3- ,3,5-tetramethyl-6-nitrospiro(indoline-2,2'- benzopyran); 1,3 ,3-trimethyl-5-methoxy- 6nitrospiro(indoline-2,2'-benzopryan); 1,3,3- trimethyl-S-carboethoxy-6-nitrospiro( indoline-2,2 benzpoyran); 1,3 ,3-trimethyl-5-chloro-6 nitrospiro(indoline-2,2'-benzopyran); 1B- carboxyethyl-3 ,3-dimethyl-6'-nitrospiro( indoline-2,2- benzopyran); l-y-carboethyoxypropyl-3,3-dimethyl- 6 '-nitrospiro( indoline-2,2 '-bensopyran); l-ycyanopropyl3,3dimethyl-6'-nitrospiro(indoline-2,2- benzopyran); and the like. Suitably these materials can be present in the photosensitive composition of this invention at a level ranging from about 1 to 8, preferably about 3 to 5, percent by weight.

As the sensitizers which can be used in this invention, suitable such sensitizers are the aromatic nitro compounds and aromatic keto compounds as 1,2- benzanthraquinon; 2,4,7-trinitro-9-fluorenone; 5- nitroacenaphthene; N-acetyl-4-nitro-l-naphthylamine; N-acetyl-4-nitro-l-naphthylamine; or N-benzoyl-4- nitro-l-naphthylamine and a photosensitive composition sensitized with one of these compounds has the sensitivity toward longer wave length end of the photosensitive wave length region at 450 m p. to 480 mp If the longer wave length end is near 430 m=, the photosensitive wave length region of the compound almost coincides with the photosensitive wave length region of the spiropyran compound and thus such a compound is unsuitable for the purpose of this invention. The amount of the sensitizer to be employed in the photosensitive composition of this invention is generally from 0.5 to percent by weight of the photosensitive resin, preferably from 2 to 7 percent by weight. Also, the spiropyran compound generally is from I to 10 percent by weight, preferably from 2 to 5 percent by weight of the photosensitive resin.

The photosensitive compositions of this invention are generally produced by the following manner. The photosensitive high molecular weight compound, the indolinobenzospiropyran compound, and the sensitizer are dissolved in a solvent such as carbon tetrachloride, trichloroethane, dichloroethylene, chlorobenzene, toluene, xylene, ethylene glycol monoethylether acetate, ethylene glycol monomethylether acetate, ethylacetate, butyl acetate, etc, and the solution is applied using conventional techniques onto conventional lithographic plates and dried. A support, for example, a metal plate such as an aluminum plate or a copper plate, or a plastic film such as a cellulose acetate or polyethylene terephthalate film can be coated to prepare a photosensitive lithographic material and dried. Suitable coating amounts are from about 0.5 to l,000g/m and for lighographic plates the coating amount generally ranges from about lg to 3g/m The photosensitive composition of this invention may contain a plasticizer such as phthalic acid alkyl diesters having 3 to 12 carbon atoms and other additives such as pigments, dyes, and the like, if desired.

When the photosensitive composition thus obtained is exposed to light such as ultraviolet light, through a photographic negative, the exposed portion is immediately colored and thus the image can be discerned as a visible image.

As described above, FIG. 3 and FIG. 4 are schematic views showing two embodiments of photosensitive materials employing the photosensitive compositions of this invention.

In FIG. 3 the light curable resin layer 32 containing dispersed therein the light coloring spiropyran compound in an encapsulated state or a molecular state is strongly bonded to a support 31 such as a metal sheet.

In FIG. 4 the light curable resin layer 43 is strongly bonded to the support 41 and also a layer 42 of a high molecular weight compound such as polyvinyl acetate,

polyethyl methacrylate, polystyrene, etc, having dispersed therein the light coloring spiropyran compound is strongly bonded to the support. The portion of layer 43 not exposed to light can be readily removed by washing the layer with an organic solvent such as benzene, toluene, xylene, dimethylsulfoxide, N,N-dimethylformamide, 'y-butylolactone, ethylene glycol monoethyl ether acetate, ethylene glycol monoethyl ether acetate, benzyl alcohol, dioxane, tetrahydrofuran, methyl ethyl ketone, acetone, ethyl acetate, etc, after light exposure.

The invention was described in detail above. Now, the invention will be explained in greater detail by reference to the following examples but these examples are intended to be illustrative and are not intended to limit the scope of the invention.

EXAMPLE] 14 g of glycidyl methacrylate, 16 g. of cinnamic acid, and 5 g of triethylamine were dissolved in 240 g of methyl ethyl ketone and after adding metallic copper to the solution, the mixture was refluxed for about l2 hours with stirring.

After the reaction was over, the low boiling compounds were distilled away under a reduced pressure and the residual product was dissolved in g of pyridine. Then, 10 g of maleic anhydride was added to the solution and the mixture was stirred for about 3 hours at 100 C. Thereafter, 500 ml of water was added to the mixture and the oily material thus formed was separated and extracted with ethyl acetate. The ethyl acetate solution was washed well with water, diluted hydrochloric acid, and then water, dried overGlaubers salt, and filtered. By distilling away the solvent from the filtrate under a reduced pressure, 37 g of a faint yellow oily material was obtained. Then, 37 g of the addition-polymerizable monomer thus obtained and 2.8 g of methyl methacrylate were dissolved in ml of methyl ethyl ketone and after adding to the solution 350 mg of N,N-azobisisobutyronitrile as a polymerization initiator, the reaction was conducted for about 5 hours at 70 C in a nitrogen atmosphere. After the reaction was over, 200 ml of methyl ethyl ketone, 2 g 5- nitroacenaphthene. 5-nitroacenaphthene. and 1.3 g of l,3,3-trimethyl-6'-nitrospiro( indoline-2,2'-

benzopyran) were added to the reaction product to provide a photosensitive liquid. When the photosensitive liquid was applied to an aluminum sheet for a photosensitive lithographic plate and dried, a coat of a photosensitive composition strongly bonded to the aluminum sheet was formed.

When the layer of the photosensitive compositionobtained. The lithographic plate thus formed was placed on an ordinary offset printing machine and printing was conducted using a commercially available ink and wetting water. The results showed that the printing plate was quite excellent in printability, image transfering property, and grease receptivity unaccompanied with the stripping of the layer and thus the employment of the photosensitive resin of this invention was superior to conventional polyvinyl cinnamate.

EXAMPLE 2 Based on the reaction procedure as described in Example l, the high molecular weight Compounds A, B, and C were prepared by employing the reaction components as shown in the following table.

Product Reaction Components Amount Compound A Glycidyl Aerylatc l4 Cinnamic Acid l5 Phthalic Anhydride l5 Compound B Glycidyl Methacrylate l4 B-(Z-FuryhacrylicAcid l4 Maleic Anhydride Compound C Glycidyl Methacrylate l4 Cinnamic Acid [5 Phthalic Anhydride 9.8

By adding 5 percent by weight of N-acetyl-4-nitro-lnaphthylamine and 3 percent by weight of 1,3,3- trimethyl-6'-nitro-8-methoxyspiro-(indoline-2,2- benzopyran) to the high molecular weight compound prepared above, a photosensitive composition was prepared.

A photosensitive lithographic plate was prepared using the photoconductive composition in the same manner as described in Example 1. By exposing the plate to light through a negative, a visible image was obtained and when printing was conducted using the printing plate and the same procedures as described in Example 1, it was confirmed that the printing plate showed excellent printability unaccompanied by the stripping of the layer.

EXAMPLE 3 14 g of glycidyl methacrylate, 16 g of cinnamic acid, and 5 g of triethylamine were dissolved in 240 g of methyl ethyl ketone and after adding to the solution 800 mg of powdered sulfur, the mixture was refluxed for about 10 hours with stirring. After the reaction was,

conducted for about 2 hours, the reaction productwas poured in 500 ml of water and 34 g of a faint yellow oily material was obtained. Using the nuclear magnetic res onance spectra and the infrared absorption spectra, the compound obtained was confirmed to be [By-dicinnamoyloxy-n-propyl methacrylate. Then, 34 g of the monomer thus produced and 2.6 g of methyl methacrylate were dissolved in 100 ml of methyl ethyl ketone and after adding to the solution 340 mg of N,N- azobisisobutyronitrile as the polymerization initiator, the reaction was conducted for about 5 hours at C in a nitrogen atmosphere.

After the reaction was over, 200 ml of methyl ethyl ketone, 1.7 g of Smitroacenaphthene, and 1.0 g of l-ycarboethoxypropyl-3,3-dimethyl-6- nitrospiro(indoline-2,2-benzopyran) were added to the reaction product to provide a photosensitive liquid.

EXAMPLE4 14 g of glycidyl acrylate, 16 g of einnamic acid, and 5 g of triethylamine were dissolved in 240 g of methyl ethyl ketone and after adding 150 mg of hydroquinone to the solution, the mixture was refluxed for about 10 hours with stirring. After the reaction was over, the low boiling compounds were distilled away under a reduced pressure and the residue was added to about 20 ml of water. The oily material thus formed was separated and extracted with ethyl ether and by treating theextract using conventional techniques, 25 g of a faint yellow oily material was obtained. By elementary analysis, infrared absorption spectra, and nuclear magnetic resonance spectra, the oily product was confirmed to be y-cinnamoyloxy-fl-hydroxypropyl methacrylate.

25 g of the monomer obtained above, 2 g of methyl methacrylate, and 1 g of acrylonitrile were dissolved in ml of tetrahydrofuran and then polymerization was conducted by adding 200 mg of benzoyl peroxide to the solution as the polymerization initiator. When the reaction was over,the reaction product was poured in nhexane to recover the polymer.

20 g of the polymer thus obtained was dissolved in 200 g of ethyl acetate and then 1 g of 2,4,7-trinitro Qfluorenone as a sensitizer and 0.8 g of 1,3,34rimethyl- 5-carboethoxy-6-nitrospiro(indoline-2,2- benzopyran) were added to the solution to provide a photosensitive liquid. The liquid was applied to an aluminum sheet and dried. When the photosensitive sheet was exposed to light, a visible image was immediately formed. When a printing plate was prepared and tested in the same manner as described in Example 1, the

printing plate was confirmed to have excellent printability.

EXAMPLES 10 g of a photosensitive resin, poly-y-cinnamoyloxy- B h ydroxypropyl methacrylate, was dissolved in methyl ethyl ketone and then 500 mg of N-acetyl-4-nitro-l naphthylamine and 300 mg of 1,3,3-trimethyl-6 nitrospiro(indoline-2,2'-benzopyran) were added to the solution to provide a photosensitive liquid. When the printing test was conducted using the photosensitive liquid in accordance with Example 1, the product was confirmed to have excellent printability.

EXAMPLE6 19 g of B-hydroxyethyl methacrylate was dissolved in 46 g of pyridine and then 25 g of B-(2-furyl)acrylic acid chloride was added incrementally to the solution at room temperature. I

After conducting the reaction for about 5 hours, the product was added to 200 ml of water and the liquid separated was extracted with ethyl ether. The ether layer formed was separated by decantation, washed with dilute hydrochloric acid and then water, dried over Glaubers salt, and filtered. By distilling away the ether from the ether layer under a reduced pressure, 33 g of a faint yellow oily material was obtained. Then, the oily product was dissolved in 200 g of tetrahydrofuran and after adding 100 mg of N,N'-azobisisobutyronitrile to the solution, the reaction was conducted for about 4 hours in a nitrogen atmosphere. After the reaction was over, the product was added dropwise to n-hexane to obtain a white polymer.

2 g of the polymer thus obtained was dissolved in about g of methyl ethyl ketone and then 10 mg of N-acetyl-4-nitro-l-naphthylamine and 50 mg of 1,3,3- trimethyl-6-nitrospiro(indoline-2,2'-benzopyran) were added to the solution to provide a photosensitive liquid. The liquid was applied to an aluminum sheet for photosensitive lithographic plate and dried. When the photosensitive plate was exposed to light, the latent image became visual immediately and thus the procedure was conducted very easily under a yellow safety lamp. The printing plate thus prepared had also excellent properties as printing plate and also it was confirmed that the photosensitive layer was particularly excellent in sensitivity.

EXAMPLE7 14 g of B-cinnamoyloxyethyl methacrylate and 2 g of methyl methacrylate were dissolved in 70 g of methyl ethyl ketone and they were reacted for about 5 hours in a conventional manner. Then, 70 g of methyl ethyl ketone, 800 mg of 5-nitroacenaphthene and 500 mg of l,3,3-trimethyl-6-nitrospiro(indoline-2,2,- benzopyran) were added to the solution to provide a photosensitive liquid. The solution was applied to an aluminum sheet for a photosensitive lithographic plate treated with a zirconium fluoride solution and dried. When the photosensitive plate was exposed to light for 40 seconds through a photographic transparent negative using a PLANO PS PRINTER A3 (made by the Fuji Photo Film Co., Ltd), the exposed portions were immediately colored. By removing the polymer at the unexposed portions with acetone, a clear image was obtained.

The printing plate thus prepared was placed on an ordinary offset printing machine and printing was conducted using a commercially available ink and wetting water. The printing plate showed excellent printability and transferring property and printed copies having clear images were obtained.

While the invention has been described in detail and in terms of specific embodiments thereof, it will be apparent that various modifications and changes can be made therein without departing from the spirit and scope thereof.

What is claimed is:

l. A photosensitive composition comprising (1) an organic solvent soluble photosensitive high molecular weight compound having therein at least one of the units represented by the following general formulae (I) to (V) Ih -CH1C E20 1 CH2 JEEP-OH CH 0CI(|3=CHRa R2 Formula (1) R1 b ...CH

I CH] O R: 1] J I HO-C- CHRa CH -OCl(l3=CH-R3 R1 7 Formula (II) B1 mmarnim l -CH2- i I H-O-U-Rr-C OOH CH1O(T(II=CH-Ra (B R.

R1 l\ hen a a. q

C 0-X(CH;-CO) J(|3=CH-Ra Formula (IV) and CH -C- OO-X(CH:)m-O(i7(lJ=CH-Ra Formula (V) wherein R represents a hydrogen atom or a methyl group; R represents a hydrogen atom, a cyano group or a -COOR group in which R represents a hydrogen atom or an alkyl group having from 1 to 6 carbon atoms; R represents a group, a

group, a

group or a group in which R represents a hydrogen atom, a halogen atom, a nitro group, a methyl group, an ethyl group, a methoxy group or an ethoxy group; R represents a hydrogen atom, an alkyl group having from 1 to 6 carbon atoms, or a halogenated alkyl group; R represents a -CH, CH group, a -CH =CH- group, or a l l Q group; X represents an oxygen atom or a group; n represents an integer of from 1 to 4; and m represents an integer of from 1 to 6, comprising a homopolymer of said units, a copolymer of said units, or a copolymer of said units and units of a monomer copolymerizable therewith; (2) a photochromic indolinobenzospiropyran compound; and (3) a sensitizer.

2. The photosensitive composition as set forth in claim 1, wherein said photosensitive composition sensitized with said sensitizer has a sensitivity toward the longer wave length end of the photosensitive wave length region at a region higher than 430 my, and also has a spectral sensitivity at a longer wave length than the photosensitive wave length region of the photochromic spiropyran compound.

3. The photosensitive composition as set forth in claim 1, wherein said photochromic spiropyran compound is sensitive to light having a different wave length from the light to which said sensitized photosensitive compound is sensitive.

4. The photosensitive composition as set forth in claim 1, wherein said photosensitive compound is solvent soluble and becomes solvent insoluble on exposure to light.

5. The photosensitive composition as set forth in claim 1, wherein said indolinobenzospiropyran compound is 1,3,3-trimethyl-6'-nitrobis(indoline-2,2'- benzopyran); 1,3,3-trimethyl-6'-nitro-8'- methoxyspiro(indoline-2,2 -benzopyran); 1,3 ,3,5- tetramethyl-6'-nitrospiro(indoline-2,2-benzopyran); l,3,3-trimethyl-5-methoxy-6'-nitrospiro(indoline-2,2'- benzopyran 1,3 ,3-trimethyl5-carbethoxy-6'- nitrospiro(indoline-2,2-benzopyran); l,3,3-trimethyl- 5-chloro-6-nitrospiro(indoline-2,2'-benzopyran); LB- carboxyethyl-3,3-dimethyl-6'-nitrospiro(indoline-2,2'- benzopyran); 1-ycarbethoxypropyl-3,3-dimethyl-6- nitrospiro(indoline-2,2'-benzopyran); or Lycyanopropyl-3,3-dimethyl-6'-nitrospiro(indoline-2,2-

benzopyran). *benzopyran).

6. The photosensitive composition as set forth in naphthylamine; or N-benzoyl-4-nitrol -naphthylamine.

7. The photosensitive composition as set forth in claim 1, wherein said indolinobenzospiropyran compound is present at a level ranging; from 1 to 10 percent by weight based on the weight of said photosensitive compound and wherein said sensitizer is present at a level of from 0.1 to 15 percent by weight based on the weight of said photosensitive compound.

8. A photosensitive element comprising a support having thereon a layer of the photosensitive composition of claim 1.

9. The photosensitive element of claim 8, wherein said support is a metal plate or a plastic film.

10. The photosensitive composition as set forth in claim 1, which comprises a homopolymer formed of said units (1), (II), (III), (IV) or (V). i

11. The photosensitive composition as set forth in claim 1, whereinsaid photosensitive high molecular weight compoundconsists essentially of a copolymer of said units (I) to (V) as essentially the sole constituents of said copolymer.

12. The photosensitive composition as set forth in claim 1, wherein said photosensitive high molecular weight compound comprises a copolymer of at least one of said units'(l) to (V) with units ofa monomer copolymerizable therewith.

13. The photosensitive composition as set forth in claim 12, wherein said monomer copolymerizable therewith is selected from the group consisting of styrene, a-methylstyrene, acrylic acid, methacrylic acid, esters of methanol, ethanol, propanlol, butanol, isobutanol, amyl alcohol, hexyl alcohol, octyl alcohol, lauryl alcohol and stearyl alcohol, acrylic acid, methacrylic acid, acrylamide, acrylonitrile, methacrylonitrile, vinyl chloride, vinyl acetate, B-hydroxycthylrnethacrylatc, N-methylolacrylamide, glycidyl methacrylate, y-chloro-fi-hydroxypropyl methacrylate, glycerol acrylate or glycerol methacrylate. 7

14. The photosensitive composition as set forth in claim 1, wherein said photosensitive high molecular. weight compound comprises a copolymer of at least one of said units represented by the general formulae (1) to (V) and units of a monomer copolymerizable therewith, the monomer copolymerizable therewith being from 2 to 35 percent by weight of the photosensitive high molecular weight compound.

15. The photosensitive composition as set forth in claim 13, wherein the monomer copolymerizable therewith is from 10 to 25 percent by weight of the photosensitive high molecular weight compound.

16. The photosensitive composition as set forth in claim 1, wherein R represents a group.

17. The photosensitive composition as set forth in claim 1, wherein R represents a group.

18. The photosensitive composition as set forth in claim 1, wherein R represents a group.

19. The photosensitive composition as set forth in claim 1, wherein R represents a group.

20. The photosenstiive composition as set forth in claim 1 consisting essentially of components (1), (2) and (3).

21. The photosensitive composition as set forth in claim 1, wherein the photosensitive high molecular weight compound has a molecular weight of from 5,000 to 50,000.

22. The photosensitive as set forth in claim 21, wherein the photosensitive high molecular weight compound has a molecular weight of from 10,000 to 25,000.

23. The photosensitive composition as set forth in claim 1, wherein said photosensitive composition has a sensitivity in the wave length region of 450 mu to 480 24. The photosensitive composition as set forth in claim 7, wherein said composition contains from 2 to 1 5 percent of indolinobenzospiropyran and from 2 to 7 percent of said sensitizer, both based on the weight of said photosensitive compound.

25. The photosensitive composition as set forth in claim 1, wherein units of formulae (1) to (V) are selected from the group consisting of:

HOCOCH=CHCOOH CH; CH;

H C OCHzCHr-C O OH COzCHJ CH CH3 26. The photosensitive composition as set forth in claim 25 which is a homopolymer.

27. The photosensitive composition as set forth in claim 25 which is a copolymer of two or more materials of formulae (a) to (0).

28. The photosensitive composition as set forth in claim 25 which is a copolymer of one of materials (a) to 0) and from 10 to 25 percent by weight of another monomer copolymerizable therewith selected from the group consisting of: styrene, a-methylstyrene, acrylic acid, methacrylic acid, esters of methanol, ethanol, propanol, butanol, isobutanol, amyl alcohol, hexyl alcohol, octyl alcohol, lauryl alcohol and stearyl alcohol, acrylic acid, methacrylic acid, acrylamide, acrylonitrile, methacrylonitrile, vinyl chloride, vinyl acetate, B-hydroxyethylmethacrylate, N-methylolacrylamide, glycidyl methacrylate, ychloro-B-hydroxypropyl methacrylate, or glycerol methacrylate, based on the total weight of the polymer.

29. The photosensitive composition as claimed in claim 1 wherein the photosensitive high molecular weight compound contains units of general formula (I).

30. The photosensitive composition as claimed in claim 1 wherein the photosensitive high molecular weight compound contains units of general formula (II).

31. The photosensitive composition as claimed in claim 1 wherein the photosensitive high molecular weight compound contains units of general formula (III).

32. The photosensitive composition as claimed in claim 1 wherein the photosensitive high molecular weight compound contains units of general formula (IV).

33. The photosensitive composition as claimed in claim 1 wherein the photosensitive high molecular weight compound contains units of general formula (V).

34. The photosensitive composition as claimed in claim 1 wherein the photosensitive high molecular weight compound, if it is a copolymer of constituents other than two or more units of general formulae (I) to (V), contains from 2 to 25 percent by weight of another monomer copolymerizable therewith. 

2. The photosensitive composition as set forth in claim 1, wherein said photosensitive composition sensitized with said sensitizer has a sensitivity toward the longer wave length end of the photosensitive wave length region at a region higher than 430 m Mu and also has a spectral sensitivity at a longer wave length than the photosensitive wave length region of the photochromic spiropyran compound.
 3. The photosensitive composition as set forth in claim 1, wherein said photochromic spiropyran compound is sensitive to light having a different wave length from the light to which said sensitized photosensitive compound is sensitive.
 4. The photosensitive composition as set forth in claim 1, wherein said photosensitive compound is solvent soluble and becomes solvent insoluble on exposure to light.
 5. The photosensitive composition as set forth in claim 1, wherein said indolinobenzospiropyran compound is 1,3,3-trimethyl-6''-nitrobis(indoline-2,2''-benzopyran); 1,3,3-trimethyl-6''-nitro-8''-methoxyspiro(indoline-2,2''-benzopyran); 1,3,3,5-tetramethyl-6''-nitrospiro(indoline-2,2''-benzopyran); 1,3,3-trimethyl-5-methoxy-6''-nitrospiro(indoline-2,2''-benzopyran); 1,3,3-trimethyl-5-carbethoxy-6''-nitrospiro(indoline-2,2''-benzopyran); 1,3,3-trimethyl-5-chloro-6''-nitrospiro(indoline-2,2''-benzopyran); 1-Beta -carboxyethyl-3,3-dimethyl-6''-nitrospiro(indoline-2,2''-benzopyran); 1- gamma -carbethoxypropyl-3,3-dimethyl-6''-nitrospiro(indoline-2,2''-benzopyran); or 1- gamma -cyanopropyl-3, 3-dimethyl-6'' -nitrospiro(indoline-2,2''-benzopyran). -benzopyran).
 6. The photosensitive composition as set forth in claim 1, wherein said sensitizer is 1,2-benzanthraquinone; 2,4,7-trinitro-9-fluorenone; 5-nitrobacenaphthene; picramide; N-acetyl-4-nitro-1-naphthylamine; or N-benzoyl-4-nitro-1-naphthylamine.
 7. The photosensitive composition as set forth in claim 1, wherein said indolinobenzospiropyran compound is present at a level ranging from 1 to 10 percent by weight based on the weight of said photosensitive compound and wherein said sensitizer is present at a level of from 0.1 to 15 percent by weight based on the weight of said photosensitive compound.
 8. A photosensitive element comprising a support having thereon a layer of the photosensitive composition of claim
 1. 9. The photosensitive element of claim 8, wherein said support is a metal plate or a plastic film.
 10. The photosensitive composition as set forth in claim 1, which comprises a homopolymer formed of said units (I), (II), (III), (IV) or (V).
 11. The photosensitive composition as set forth in claim 1, wherein said photosensitive high molecular weight compound consists essentially of a copolymer of said units (I) to (V) as essentially the sole constituents of said copolymer.
 12. The photosensitive composition as set forth in claim 1, wherein said photosensitive high molecular weight compound comprises a copolymer of at least one of said units (I) to (V) with units of a monomer copolymerizable therewith.
 13. The photosensitive composition as set forth in claim 12, wherein said monomer copolymerizable therewith is selected from the group consisting of styrene, Alpha -methylstyrene, acrylic acid, methacrylic acid, esters of methanol, ethanol, propanol, butanol, isobutanol, amyl alcohol, hexyl alcohol, octyl alcohol, lauryl alcohol and stearyl alcohol, acrylic acid, methacrylic acid, acrylamide, acrylonitrile, methacrylonitrile, vinyl chloride, vinyl acetate, Beta -hydroxyethylmethacrylate, N-methylolacrylamide, glycidyl methacrylate, gamma -chloro- Beta -hydroxypropyl methacrylate, glycerol acrylate or glycerol methacrylate.
 14. The photosensitive composition as set forth in claim 1, wherein said photosensitive high molecular weight compound comprises a copolymer of at least one of said units represented by the general formulae (I) to (V) and units of a monomer copolymerizable therewith, the monomer copolymerizable therewith being from 2 to 35 percent by weight of the photosensitive high molecular weight compound.
 15. The photosensitive composition as set forth in claim 13, wherein the monomer copolymerizable therewith is from 10 to 25 percent by weight of the photosensitive high molecular weight compound.
 16. The photosensitive composition as set forth in claim 1, wherein R3 represents a
 17. The photosensitive composition as set forth in claim 1, wherein R3 represents a
 18. The photosensitive composition as set forth in claim 1, wherein R3 represents a
 19. The photosensitive composition as set forth in claim 1, wherein R3 represents a
 20. The photosenstiive composition as set forth in claim 1 consisting essentially of components (1), (2) and (3).
 21. The photosensitive composition as set forth in claim 1, wherein the photosensitive high molecular weight compound has a molecular weight of from 5,000 to 50,000.
 22. The photosensitive as set forth in claim 21, wherein the photosensitive high molecular weight compound has a molecular weight of from 10,000 to 25,000.
 23. The photosensitive composition as set forth in claim 1, wherein said photosensitive composition has a sensitivity in the wave length region of 450 mu to 480 mu.
 24. The photosensitive composition as set forth in claim 7, wherein said composition contains from 2 to 5 percent of indolinobenzospiropyran and from 2 to 7 percent of said sensitizer, both based on the weight of said photosensitive compound.
 25. The photosensitive composition as set forth in claim 1, wherein units of formulae (I) to (V) are selected from the group Consisting of:
 26. The photosensitive composition as set forth in claim 25 which is a homopolymer.
 27. The photosensitive composition as set forth in claim 25 which is a copolymer of two or more materials of formulae (a) to (o).
 28. The photosensitive composition as set forth in claim 25 which is a copolymer of one of materials (a) to o) and from 10 to 25 percent by weight of another monomer copolymerizable therewith selected from the group consisting of: styrene, Alpha -methylstyrene, acrylic acid, methacrylic acid, esters of methanol, ethanol, propanol, butanol, isobutanol, amyl alcohol, hexyl alcohol, octyl alcohol, lauryl alcohol and stearyl alcohol, acrylic acid, methacrylic acid, acrylamide, acrylonitrile, methacrylonitrile, vinyl chloride, vinyl acetate, Beta -hydroxyethylmethacrylate, N-methylolacrylamide, glycidyl methacrylate, gamma -chloro- Beta -hydroxypropyl methacrylate, or glycerol methacrylate, based on the total weight of the polymer.
 29. The photosensitive composition as claimed in claim 1 wherein the photosensitive high molecular weight compound contains units of general formula (I).
 30. The photosensitive composition as claimed in claim 1 wherein the photosensitive high molecular weight compound contains units of general formula (II).
 31. The photosensitive composition as claimed in claim 1 wherein the photosensitive high molecular weight compound contains units of general formula (III).
 32. The photosensitive composition as claimed in claim 1 wherein the photosensitive high molecular weight compound contains units of general formula (IV).
 33. The photosensitive composition as claimed in claim 1 wherein the photosensitive high molecular weight compound contains units of general formula (V).
 34. The photosensitive composition as claimed in claim 1 wherein the photosensitive high molecular weight compound, if it is a copolymer of constituents other than two or more units of general formulae (I) to (V), contains from 2 to 25 percent by weight of another monomer copolymerizable therewith. 